Amino-triazol derivatives



United States Patent O 3,121,695) AMENG-TRIAZGL Martians JohannesKooprnans, leagues Meitzcr, Henderixus @hias Heisman, BeiuardnsGerhardus van den Bos, and Kohus Wellinga, all of Van Houteniam, Weesp,Netherlands, assiguors to North American Philips Company, inc, New York,N.Y., a corporation of Delaware Filed Apr. 22, 1953, Ser. No. 735,139Claims priority, application Netherlands Apr. 27, 1957 it; Claims. (Cl.26%--3%S) The invention relates to a. method of producing newamino-triazol derivatives. From laboratory experiments it has *beenfound that these products are suitable for combating noxious organisms.

The invention is characterized in that a X=P- leriratire of anamino-triazol of the general formula a tautomeric form or a salt ofeither of them is caused to react with a compound of the generalformula:

in which formulae R designates a hydrogen atom or an all yl-,cycloalhyl-aiylor aralhy group, in which groups one or more substituentsand/ or unsaturated bonds may be contained, R R R and R designatealiphatic hydrocarbon radicals, X designates a double-bonded oxygenorsulphur atom md l-Ilg a halide atom, for example a chlorine or bromineatom, so that a product is obtained, in which the hydrogen atom bound tonitrogen in the amino-triazol ring is replaced by the his(N.N.-dialkylamido)-phosphorylor -thiophosphoryl-group, in such a waythat the phosphorous atom is bound to a nitrogen atom of the triazolring.

It has been found that reaction products with attractive properties areobtained, in particular, if 3-aminol.2.4-triazol or a derivative thereofaccording to the definition of the invention is used as a startingmaterial, in which R is an aliphatic hydrocarbon radical having 1 to3,l2l, Patented Feb. ll, i

8 carbon atoms, a phenyl group, 4-chloro-phenyl-, 4-mothoxy-phenyl-,carboxy-alkyl-, benzylor styryl-group. in the phosphoryl orthiophosphoryl-compounds R R R and R are preferably aliphatichydrocarbon radicals having 1 to 5 carbon atoms, particularly methylgroups. The method is preferably carried out with bis(N.N-dialkyl-amido)-phosphorylor -thiophosporyl-chloride.

As a salt of 3-amino-triazol 1,2,4 or of the It -derivative may be used,for example, the hydrochloric acid salt, the sulphuric acid salt or thebisulpha-te.

in the cases, in which the starting material is 3-aminotriazol 1.2.4,the R derivative thereof or the salts of an acid, for examplehydrochloric acid or sulphuric acid or the bisulphate of one of them,the choice of the solvent is primarily determined by the solubility of3-arnin-o .triazol 1.2.4 or the R derivative thereof, since thephosphorylor thiophosphoryhcompounds employed in accordance with theinvention are satisfactorily soluble in a great many of the conventionalsolvents.

in these cases suitable solvents are: liquid aliphatic hydrocarbons, forexample petroleum ether, ligroin, hexane, cyclohexane, aromatichydrocarbons, for example, benzene, toluene, xylene; aliphatic others,for example diethyl ether, methyl-ethyl ether, diisopropyl ether,tetrahydrofurane, tertiary amines, for example, triethylamine pyridinepicolines, lutidines or collid-ines or mixtures thereof. As a suitablesolvent may be mentioned acetonitril. If desired, lower aliphaticketones may be used, for example, acetone or methyl-ethyl ketone, but inthis case, it should be considered that these solvents can react withthe triazol-derinative whilst forming a Sch-iffs base. Other solventsare ethylacetate, ethyl-forrniate, nitrobenzene, carbon tetrachlorideand dimethylformamide.

In general, aminostriazol and derivatives thereof, of which the group Rcontains more than 5 carbon atoms, are better soluble in liquids :oflower polarity. For this reason, when using these amino-triazolderivatives, it is to be preferred to use aliphatic or aromatichydrocarbons or others over the other aforesaid of higher polarity. Thelatter groupqof solvents may be often used successfully, if anamino-triazol is used as a starting material, in winch R is hydrogen ora carbon chain having less than 5 carbon atoms. Mention may be made ofacetonitril and furthermore a liquid tertiary amine, preferably pyridineor the homologues thereof: the picolines, lutidines and collidines.

It should otherwise be noted that, for a successful reaction, it is,indeed, desirable but not necessary that the two reaction componentsshould be in a completely dis solved state from the start of theprocess. The reaction is also accomplished, if, for example, the triazolderivative is contained partly in the diluent in a roughly dispersedstate.

It is furthermore important to carry out the reaction in the presence ofan acid binder. The aminotriazol or IR -derivative thereof, used asstarting material, may serve as such, in which case an excess quantityof this compound is employed.

'A group of acid binders which may be successfully used, are amines andparticularly tertiary amines, for example of the group consisting oftriallzylamines, NN- dialkylanilines; trimethylamine, triethylamine,d-iethylanline and furthermore pyridine or homologues thereof, forexample the picolines, lutidines or collidines and furthermoretriethanolamine. As a primary amine use may be made of ethanolamine, asa secondary amine for example diethanolamine. Even the amino-triazolderivative, which is the starting material and which is obtained by thereaction according to the invention may operate as an acid binder. ingeneral, use will be made of a ,uantity of acid binder which isequivalent to the quanit an excess quantity of 3-amino-l.2.4 triazol oran R derivative thereof or of the said amines are used as an acid binderthe reaction is preferably carried out at a temperature lying betweenand 86 C., for example, at a temperature of about 40 C. to 70 C.

After the termination of the coupling reaction between the aminotriazolor an R -derivative thereof with the phosphorylhalide or thethio-phosphorylhalide it is adable to purify the reaction product. Thismay be carried out by removing the solvent, for example by evaporationin vacuo. The residue, which contains apart from the reaction productthe hydrogen halide salt of the acid binder and, as the case may be,unchanged starting material may then be extracted with a suitablesolvent, for example an aromatic or aliphatic hydrocarbon, such astoluene, xylene, benzene, hexane, petroleum ether, ligroine or analiphatic ether, for example, ethyl ether or dimethyl ether. From theextract thus obtained, which is substantially free from the salt of theemployed acid binder, the purified reaction product may be obtained byconventional purifying methods, for example, recrystallisation. if theamino-triazol derivative contained a group R with more than 4 carbonatoms, the aforesaid extract may be purified by washing it with Water.With this treatment an excess quantity, if any, of phosphorylorthiophosphoryl-cornpound, as well as the acid binder, if at east thelatter compound is soluble in water, are removed.

lt has furthermore been found that very satisfactory results areobtainable when using a different group of acid binders. This groupcomprises metal compounds and ammonium compounds, which are suitable tobind the hydrogen halide set free during the reaction according to theinvention; with particular advantage there may be used those ofalkaline-earth metals, for example, those of calcium and barium and,particularly those of alkali metals, for example those of sodium andpotassium. As metal compounds may be used oxides, hydroxides,carbonates, bicarbonates, alcoholates and metal salts of carboxylicacids for example acetates and propionates, for instance sodium-,potassium-, calcium-, magnesiumand zinc-hydroxide, calcium-, bariumandzinc-oxide, sodiumand potassium-carbonate and -bicarbonate, magnesiun1-,calciumand barium-carbonate, sodiumand potassiumalcoholates and sodiumacetate. As ammonium compounds use may be made of ammonia,ammonium-carbonate and -acetate.'

Suitable acid binders in accordance with the method invention are themetal hydroxides, particularly calciumand bariumand particularlysodiumand potassium-hydroxide. Very satisfactory acid binders are, fur-With the reaction according to the invention of 3- amino-triazol-l.2.4or the P. -derivative thereof with a phosphorylor thiophosphoryl halidein the presence of a metal compound as an acid hinder, the metal halideis separated out. This reaction may be carried out in different ways.

A suitable method is that in which as an acid binder use is of an alkalimetal alcohclate. In this case, preferably the 3-amino-triazoi-l.2.4 orthe Bi -derivative thereof is dissolved in a solution of alkali metalalcoholate in anhydrous alcohol, articularly a lower alcohol moreparticularly methanol or ethanol, to which is added the phosphorylhalide or thiophosphoryl halide derivative. The alcoholate may beformed, for example, by dissolvine the alkaline netal in the alcohol tobe used as a solvent.

d derivative thereof is dissolved in a polar organic solvent, in whichth metal hydroxide is dissolved, or suspended in a finely divided state,after which the phosphoryl halide or the thiophosphoryl halidederivative is added.

The metal hydroxides are particularly those of sodium potassium andthose of calcium and barium. When using sodiun or potassium hydroxide,it is advantageous to use, as a polar organic solvent, a lower alcohol,for example methanol or ethanol, since these hydroxides are soluble inthese alcohols. The reaction is then carried out in a homogeneousmedium.

It has been a surprise to find that the reaction according to theinvention may yield, moreover, very satisfactory results of, as an acidbinder, use is made of aqueous alkalineearthor alkaline-hydroxides. Onemethod Whicn yields particularly satisfactory products according to theinvention in substantially theoretical quantities is that in which the3-amino-triazol-'1.2.4 or the R derivative thereof is dissolved in amixture of a polar organic solvent, preferably a lower alcohol, forexample metha nol or ethanol and, for example, the theoreticallyrequired quantity of alkali-hydroxide, for example as a 30 to 50% byWeig t solution is dissolved in water, to which the phosphoryl halide orthe thiophosphoryl halide is added. Particularly satisfactory resultsare obtained by using a mixture of methanol or ethanol and 3G to 50%aqueous solution of sodiumand potassium-hydroxide. In these cases,yields of to of the desired product may be obained. The termtheoretically required quantity of all herein the quantity required tobind the maximum quantity of hydrogen halide set free during thereaction.

The use of alkal'-metal hydroxides as acid binders and the use ofloweralcohols as solvents are advantageous to the technical performance ofthe reaction, since in this case the reaction takes place in ahomogeneous medium. An advantage of the use of an aqueous solution ofalkalihydroxide over that of solid alkali-hydroxide is that in the firstcase a homogeneous solution is obtained immediately after mixing. Whenusing solid alkali-hydroxide some time passes before it is dissolve Forcarrying out the reaction according to the invention, in which metalcompounds are used as acid binders, use is preferably made of polarsolvents, for example alcohols such as pro anol, isopr-opanol, butanol,secondary butanol and iso-butanol and particularly, methanol or ethanoland ketones such as acetone and methyl-ethyl ketone or acetonitril. Evennon-polar solvents such as aliphatic hydrocarbons and aromatichydrocarbons, for example benzene, toluene or xylene may be used. Since,

however, the metal compound to be used as an acid binder is solubleherein only with difliculty, the reaction is performed less smoothly inthese cases. 7

The yields of compounds according to the invention usually exceed, whenmetal compounds are used as acid bin ers and when polar solvents areused, as a rule those obtained when amines are used as'acid binders.These higher yields, which attain the theoretical values, are to beascribed, inter alia, to the simplicity of the Working at up andpurification of the reaction product and, probably particularly to thesmooth'reaction even at a low temperature, so that no or substantiallyno by-products will be formed.

it is that the phos horyl chlorides and thiophosphoryl chloride as acidchlorides, are sensitive to the found that even satisfactory results maybe obtained, when a the reaction according to the in ention is carriedout with a suspension of 3-amino-triazol-l.2.4 or the R derivativethereof in a concentrated aqueous solution or susof alkali metal oralkaline earth metal hy' .l "e. carrying out the reaction according tocritic-n in a 33% aqueous sodiumor potassium- -hydroxide is to beunderstood to mean hydroxide solution, yields of 70 to 80% of thedesired products were obtained.

With this method the compounds according to the invention, in which Rdesignates an alkyl group with at least 5 carbon atoms or a cycloalkyl-,aralkylor arylgroup, can be separated out in a very simple manner afterthe reaction has terminated, since they separate out in a finelydivided, solid state.

The method according to the invention in which a metal compound is usedas an acid binder, provides, as a rule, a smooth reaction and may becarried out at normal temperature. The reaction temperature ispreferably chosen to be slightly lower, for example between and +10 C.;this particularly obtains, if the reaction is carried Out in an aqueousand particularly a homogeneous medium.

It has been found that the method according to the invention, in whichmetal compounds are used as acid binders and the methods in which aminesare used for the same purpose, yield the same products.

3-amino-triaZol-1.2.4 and R derivatives thereof have a somewhatamphoteric nature. This means that there may exist not only salts of,for example, hydrochloric acid, but also metal salts. Therefore it isnot impossible that, in those cases in which a metal compound, forexample sodium is used as an acid binder, at least partly the sodiumsalt of the employed amino-triazol should be formed, which might reactwith the phosphoryl halide or thiophosphoryl halide. For example thesodium salt of a 3-anino-triazol-1.2.4 may be separated out byevaporating an alcoholic solution of sodium alcoholate and a 3-amino-triazol-l.2.4 until no alcohol can any longer be removed. If thesodium salt of the 3-amino-triazol-1.2.4 derivative thus obtained issuspended for example in benzene and if the suspension obtained isheated for some time, after the addition of a phosphoryl halide, asatisfactory quantity of a compound according to the invention isobtained.

it should be noted that the amino-triazol and the said erivativesthereof, employed in accordance with the invention, may occur intautomeric forms. This means that the hydrogen atom bound to one of thenuclear nitrogen atoms does not occupy a fixed position. In order to fixthe idea, the amino-triazol or a derivative thereof in accordance withthe present application is assumed to be given by a formula in whichthis hydrogen atom is bound to the nitrogen atom indicated by ring atomnumber 4. in accordance with conceptions expressed in literature thisdoes not mean, however, that this hydrogen atom could not be bound toany of the other atoms of the amino-triazol (J. Or Chem, X /lll, page196 (1953)).

The tautomerism with amino-triazol-l,2,4 and R derivatives thereofinvolves that it cannot be stated with the reaction products thereofwith his (N.N-diallryl-amido)- phosphoryl halides, with which of thethree nitrogen atoms in the triazol-ring the phosphoryl-group is bound.From the experiment, which led to the invention, it has been found thatwith a definite reaction mainly one product is always formed, which hasa well-defined melting point, as will be evident from the examples to bedescribed hereinafter.

Among the amlno-triazol derivatives to be used in accordance with theinvention there are known the compounds in which R-=H, CH (3 1-1 (1 1-1iso-C l-l iso-C H n-pentyl, n-hexyl wd phenyl. The further compounds inwhich R may be, for example, butyl, heptyi, aralkyl, and so on, may bereduced from an aminoguanidine salt, for example the nitrate, bisulphateor sulphate and a carboxylic acid of the formula R COOH or thecorresponding acid halide, preferably the acid chloride. For theproduction of the amino-triazol itself the principle of this method isdescribed in Organic Synthesis 26, page 11. Thebis-dialltyl-phosphorylhalide and the corresponding thio-compounds maybe produced by a method as indicated in the German patent specificationNo. 900,814.

In accordance with the invention it has now been found that the productsobtained by the method according, to the invention have as is shown bylaboratory experiments, an activity against noxious organisms,especially against particular fungi and insects and, moreover, redspider mites.

It has particularly been found that many compounds have an activityagainst fungi of the family of the Erysiphaceae. To this family belong,for example, the kinds:

([1) Sphaerotheca pannosa (Walln) Lv (rose),

(b) Erysiphacichoracearum D.C.cucumber, potato,

salad, sunflower, tobacco,

(c) Erysiphc polygony D.C.clover and other leguminoses,

(d) Uncimzla necator (Schw.) Burn-grape,

(e) Erysiphe graminis D.C.cereals,

(f) Splmeroflzeca moi's zzml (Schw.) Berk.-gooseberry,

(g) Podosphaera leucotricha (Ell et Everh) Salm. apple, pear. After thenames of the fungi there are indicated the plants on which thecorresponding fungi may occur.

Plants, of which the overground parts were sprayed by a productaccording to the invention, were appreciably less af ected by theaforesaid fungi than untreated plants.

A protection from the effect by these fungi was also observed when aproduct obtained in accordance with the invention was inserted into theroot system of the plant (emphytical effect).

The said fungicidal effect is particularly manifest with those reactionproducts which are obtained by causing an amino-t iazol, in which thegroup R designates a hydrogen atom, a lower aliphatic radical having 1to 8 carbon atoms or a phenyl group to react with a his(N.N-dimethylamiclo)-phosphoryl-halide, preferably the chloride.

The experiments by which the aforesaid fungicidal effect was stated werecarried out as follows.

Young barley plants (Hoi-deum vulgare) were cultivated at a temperatureof 1 C. to 18 C. in small flowerpots until the plants had a length ofabout 7 cms. Then solutions of the compounds to be tested in acetone ofdifferent concentrations were sprayed on them. As a rule, a series ofdilutions comprises solutions containing 1000, 100 or 10 mgs. of activecompound per litre. Seven plants in one pot were sprayed simultaneouslywith 0.2 ml. of the solution. T he experiment was repeated twice with 7plants each. In total 21 plants were thus treated with the same liquid.Immediately after the treatment with the solution, the plants weredusted with viable sporules of Erysiphe graminis mildew by putting thepots of the whole test series simultaneously under a spaceousbell-glass, into which, by means of a flow of air brushing past stronglyinfected leaves of barley, were distributed the sporules of mildew. Theplants were left to themselves for some time, so that the sporulessettled down uniformly on the plants. The plants were then put into aspace having a temperature of 18 C. to 20 C. and a relative humidity ofabout under a continuous illumination by fluorescent tubes (white light)having an intensity of about 300 lux. Five days after the inoculationdistinct spots of the mildew fungus had been formed on the test plantsnot treated with an active compound these spots giving 05 a fair momentof sporules.

The extent of the damage of each plant was expressed by a numeral of theseries 0 to 10, 0 being equal to no effect and 10 '1T162.illDg that thewhole leaf was covered with stains.

Per concentration-'21 statements-the numbers obtained were added.

Since the various substances were tested at different dates, which mightaffect the results, the measure of damage of each plant was alwayscompared with the one obtained when 2,4-dinitro-6(l'-methylheptyl-l-phenylcrotonate) was used as a protecting compound.Those doses were therefore each time determined which resulted V corned.

7 both with the compound to be tested and with thephenylcrotonate-derivative, in a protection of 50% for the plant. Thequotients of these doses are indicated in Table I (FIG. 1) column It.With a higher quotient the fungicidal effect of the tested compound is,therefore, also higher.

In this table the column a indicates the numeral of the example, inwhich the production or the tested aminotriazol-derivative is described.The columns 5 to g indicate the kind of substituents X and R to R Columnit shows the antieryisphaceaes effect as compared with 2,4- dinitro-6-1-methylheptyl)-1-phenylcrotonate (on barley plants). In column i meansthat a dose of mgs. of the tested compound per pot (in which wascultivated tomato, oat plants, garden beans, chickweed or beets)produces chlorosis. The reference has the op; osite meaning. Column 1'mentions the extend of leaf burning with a spraying of 1% of aqueousemulsion or a solution of the substance on tomato, oats, garden beans,chickweed or beet. means: no damage; i is: little damage and is: fairlyheavy damage. Column k finally indicates the toxicity for warrnbloodedanimals. The numbers indicated are the doses in rug/kg. mice (testanimals), producing a kill of of the animals upon oral application (LDIt has furthermore been found that the reaction products obtained inaccordance with the invention have also an activity against insects, forexample Musca domestz'czz L, Sitoplzilus granarius L, Leptr'norarsadecemlz'izeaza Say, A phz's fabae Scop. The active compounds constituteboth contact poisons and stomach poisons for the insects. It was,moreover, stated that leaf-eating and juice-sucking insects on theoverground parts of plants are killed, if the reaction products obtainedin accordance with the invention are inserted into the root system.

This insecticidal eifect occurs particularly with those compoundsaccording to the invention which are obtained by the reaction of anamino-triazcl derivative, according to the invention, in which Rdesignates a hydrogen atom or an aliphatic hydrocarbon radical having 1to 5 carbon atoms or a phenyl radical, with a hisILN-dirnethylamido)-phosphorylor thiophosphoryl-halide.

lt has furthermore been found that the products ob tained in accordancewith the invention also have an activity against mites (acari)particularly red spider mites (Tetranychidae). This activity occurs withthe same products of which the insecticidal efiect is described above.

The tests to determine the insecticidal and acaricidal effects werecarried out as follows.

Broad bean plants (Vicia fzrea L) were immersed into emulsion or asolution of the compound to be tested in water. The comuour ure employedwith the following concentrations: 0, 300, 100, 30 30 Figs. per litre(p.p.rn.). After the er or the solution had dried on. the plants, theywere infected with adult, unwinged to e black bean louse (A s fabricSeep). Similar experiments were carried out v. bush bean plants(Piasecii vtzigares L), wl ch were infected vith adult female bean redspider (Te! iizychzzs ztrzz' Koch).

At the same time test experiments were carried out, the kill of insectsand red spider mites on the untreated plants is calculated in the killpercentages in accordance with Abbotts formula. This formula goes:

X 100 .illl percentage plants and b the number of survivors or theobject con- With a second series of an secticidal effect of thesubstances obtain d in acco.

e with the of invention was :n e; riments same lends of o a nose animalswere used, but in this case the plants were cultivated in paral'linedcaper beakers, filled with washed sand. The plants were fed on aso-called linopps nutrient solution. One litre of this liquid contains0.25 g. of magnesium sulphate, 1.0 g. of calcium nitrate, 0.25 g. ofprimary potasium phosphate, 0.12 g. or" potasium chloride, a supply offerrichloride and otherwise water (Konlngsberger, Leerboek der algemenePlantkunde, Vol. ll, page 465 (1942), Amsterdam).

To the beakers was added a solution or an emulsion of the compound to betested in Water. The doses employed were: 62.5, 12.5, 2.5, 0.5 and 0.1rngs. of compound per beaker. By screening off the beakers the plantswere protected from the vapour of the compound concerned. Then theplants were infected with plant lice and red spider mites respectively.

With the two se 'es of experiments it was determined how many insects ormites were killed three days after the initiation of the infection. Thekill on check plants was deducted therefrom. When the kill percentagewas to this was indicated by the sign a percentage of less than 90%, butmore than 50% was indicated by i. A ill percentage of less than 50% wasindicated by The results of these experiments are indicated in Table ll(PEG. l-l In the first left-hand column the Roman ciphers refer to theexamples in which are described methods or producing those startingproducts in which the substituents X, R R R R and R are indicated in thefollowing six columns. In the head column entitle An/22's fabae Scop thesubcolumn A relates to the so-called, immersion effect and the subcolumnB to the emphytical insecticidal effect. The numbers 1000, 300, 100, 30,10 indicate the concentrations in mgs. of tested compound per litre(p.p.m.) with which the immersion experiments were carried on Thenumbers 62.5, 12.5, 2.5, 0.5 and 0.1 indicate the quantitles of testedcompound (in tags.) which were added to each beaker with the emphytlcaltests. The column Tetmnychus urticae Koch must be understood in a simiTo this end they are mixed with solid or liquid car-' riers or as thecase may be, dissolved therein and, if desired enriched v dispersionagents, emulsifiers .or wetting agents. sera ed, pulverized or nebulizedin air, either assuch or emulsified or dispersed in a liquid, forexample water.

Preparations which may be obtained by means of the,

active compounds are, amongst others, the mixahle oils, spray powdersand dust powders. These forms are referred to only by way of example andshould not restrict the invention thereto.

in order to produce miriable oils, the active compound is dissolved in asuitable solvent which is purely soluble vith water, to which solutionis added an emulsifier.

Suitable solvents may be Xylene, toluene,'dio:-;ane,petr I learndistillates rich in aromatic compounds, for example solvent naphtha,distilled tar oil, tetraline, cyclohexane or mixtures of these liquids.alkylphenoXy-polyglycol ethers, poly-oXyethylene-sorbitane esters offatty acids or poly-oxy-ethylene 'sorbi tol esters of fatty acids. Aplurality of these kinds of emulsifcrs are known under the tradename ofTriton, Tween and Atlox.

The concentration of active compound in the purely" water-soluble liquidis not subjected to narrow limits. i

it may fluctuate, for example, between 2 and 50% by weight. Prior to theuse of these solutions, the mixable oils are emulsified in Water and theemulsion is sprayed T Preparations thus obtained may be,

As emulsifiersmay be used ll out. As a rule, the concentration of activecompound in these aqueous emulsions lies between 0.01 and 0.5% byweight.

The spraying powders may be produced by mixing and grinding the activecompound with a solid, inert carrier, as a rule, in the presence of adispersion and/ or wetting agent. Prior to use the spraying powders aredispersed in a liquid, preferably in water; the dispersion is sprayedout. It is important that the spraying powder should consist of smallparticles in order to avoid obturation of e aperture of the volatilizer.It is therefore advisable to use, as a carrier, 2. fine, pulverulentmaterial. If desired, the mixture of carrier material, active compoundand auxiliary substances, if am is ground.

As a carrier there may be used, for example, alumina, diatomaceousearth, kaolin, dolomite, talcum, gypsum, chalk, bentonite, attapulgite,infusorial earth, Celite, wood flour, tobacco dust or ground coconutshells. Suitable dispersion agents are lignine sulphonates andnaphthalene sulphonates. As wetting agents may be used fatty alcoholsulphates, alkyl-arylsulphonates or fatty acid condensation products,for example those known under the trade name of Igepon.

Also in the dust powders the concentration of active compounds is notsubjected to narrow limits; as a rule, the concentration will be chosento lie between and 80% by weight.

The dust powders may be produced by applying the active compound as suchor dissolved in a solvent to a solid carrier. During the use thepreparation thus obtained is pulverized in a dry, finely pulverulentstate, in the air. With a choice of suitable, light carrier materials,these powders may, as an alternative, be produced in the mannerdescribed for the production of spraying powders. As carriers use may bemade of the products referred to above with the production of sprayingpowders. Usually, the concentration of active compounds in the dustpowders is lower than that in the spraying powders or mixable oils, buthigher than that of the active compounds in dispersion agents oremulsifiers, obtained by diluting spraying powders or mixable oils withliquids. The dust powders contain frequently 1 to 20% of activecompound. It may be redundant to observe that the mixable oils, sprayingpowders or dust powders according to the invention may be produced bymixing two mixable oils (or spraying and dust powders), containing eachone of the active compounds.

In the following examples methods for the production of compoundsaccording to the invention will be described. In these examples ether isto be understood to mean diethyl ether and alcoho to mean ethmol.

Example I To a mixture of 134 gs. of 3-amino-triazol1,2,4, (1.6 mol) 194gs. of collidine (1.6 mol) and 1.6 l. acetonitril is added in drops, atroom temperature, 273 gs. of bis (NJN dimethyl amide) phosphorylchloride(1.6 mol). The mixture is then kept at the same temperature for sixhours. During the addition and the further reaction the mixture isstirred. The acetonitril is then distilled 013? in vacuo. The residue isextracted with benzene. The solution thus obtained is thickened to asmall volume. A product is thus crystallized out. After rerystallizationfrom the same solvent a substance is obtained, of which the analysisshows that 1 mol of aminotriazol has reacted with 1 mol of thephosphorylchloride derivative. Yield, 52%. Melting point, 136.5 to 138C.

Analysis. Calculated: P=14.19%. 14.2%.

Remark: The calculated values of the contents of the various elements inthe products obtained, indicated in this example and in the followingexamples relate always to a compound of 1 mol amino-triazol derivativeand 1 mol of the derivative of the phosphoryl halogenide.

Found: P:

in Example II Whilst stirring to a mixture of 54 gs.5-methyl-3-aminotriazol-1.2.4 (0.55 mol) (Thiele, Heidenreich: Berichte26, page 2599 (1893)), 67 gs. of collidine (0.55 mol) and 300 mls. ofacetonitril is added in drops 94 gs. of bis (N.N-dimethylamido)phosphorylchloride (0.55 mol). The mixture is then stirred further for3.5 hours at a temperature between 60 and 70 C. The acetonitril is thenevaporated in vacuo. The residue is extracted with ether. The etherealsolution is thickened and the crystalline mass obtained isrecrystallized from ligroine and a mixture of petroleum-ether and ether.

The analysis indicates a reaction between equimolar quantities of theamino-triazol and phosphorylch-loride derivatives.

Yield, 53%. Melting point, 91 to 92 C.

Aizalysis.Calculated: P=13.34%, C=36.20%, H: 7.38%, N:36.19%. Found:P:13.3%; C=35.66%, 35.40%; H=7.53%, 7.51%; N=36.22%, 36.33%.

Example III 7.5 gs. i 5-ethyl-3-amino-triazol-1.2.4 mol) (Reilly,Madden, J. Chem. Soc. (1929), page 816), 7.2 gs. of2.6-dimet11yl-pyridine ,4 mol) and 100 mls. of acetonitril are mixed. Tothe mixture is added in drops, whilst stirring, 11.4 gs. of his(N.N-dimethyl-amido)- phosphorylchloride (V mol). After the acidchloride has been added completely, stirring is continued at roomtemperature for seven hours. Then the acetonitril is distilled ofi invacuo. The residue is extracted with acetone. The solution thus obtainedwas evaporated; the crystalline residue is extracted with benzene. Thebenzene is evaporated and the crystalline product obtained isrecrystallized twice from ligroine. The analysis exhibits that equimolarquantities of starting material have reacted with one another.

Yield: 50%. Melting point, 92 to 95 C.

Analysis.Calcul-ated: P=12.58%, C=39.02%, H: 7.78%, N=34.12%. Found: P=2.7%; 6.89%, 36.76%; H=7.7l%, 7.97%; N=33.78%, 34.22%.

Example IV 13 gs. of 5-(l'-methyleti1yl)-3-amino-triazol-l.2.4 (0.1 mol)(Reilly, Drumm: J. Chem. Soc. (1925) page 1731), 20 :gs. of his(N.N-dimethylamido)p hosphorylchloride (0.12 mol) and 12.1 gs. oftriethylarnine (0.12 mol) are mixed with mls. of acetonitril. Themixture is heated, wh lst stirring at 60 to 65 C. for five hours. Thesolvent is then distilled off in vacuo. The residue is extracted withacetone. The acetonic solution is inspissated in vacuo and the residueis twice recrystallized from ligroine and once from carbon disulphide.Yield, 50%. Melting point, 101 to 105 C. For analyzing purposes a smallqauntity of substance is recrystallized from carbon clisulphide. Melt ngpoint, 105 to 106 C.

Analysis.-Calculated: P:11.90%, C=41.53%, H: 8.13%, N=32.29%. Pound:P=12.1%; C=40.95%, 41.11%; H=8.32%, 8.20%; N:33.49%, 33.96%.

Example V To a mixture of 30.8 gs. of 5-n.pentyl-3-amino-triazol- 1.2.4(0.2 mol) (Kai er, Peters: iournal Org. Chem. 18, page 196 (1953)), 18.6gs. of colli ine (0.2 mol) and 200 mls. of acetonitril is added indrops, at normal temperature whilst stirring, 42.5 gs. of his(NN-dimethylamido)-phosphorylchloride (0.25 mol). Then the mixture isheated at 60 to 70 C. for three and a half hours. When adding acetone,the hydrochloric acid salt of collidine is separated out. It is filte edofi. The filtrate is inspissated in vaouo; the residue extracted withbenzene, the benzene solution washed, in succession, with 0.5 Nhydrochloric acid, water, a solution of sodium bicarbonate and finallyagain water. The solution is then dried and inspissated. The residue, acrystalline mass, is recrystallized four times from petroleum ether.

Exa/"nple VI A mixture of 86 gs. (0.5 moi) of amino-guanidinebisu-iphate (melting point 158 to 160 C.), 72 gs. of caprylic acid (0.05mol), 20 mls. of water and a few drops of concentrated nitric acid (SW.1.4) is heated on an oil bath at 130 to 140 C. for 50 hours.

The reaction mixture is poured out in 200 rnls. or" water after thereaction Was terminated, in a porcelain dish; it is neutralized with 60(more than 0.5 moi) of anhydrous sodium carbonate until the reaction Wasweak alkaline and the mixture was evaporated to dryness. The semi-solidrnass obtained is extracted with dry be -zene and the benzene isdistilled off. The crude substance is converted into the nitric acidsalt and recrystallized from Water. The melting point of the nitrate is14 C; with the calculated quantity of methanolic potassium hydroxidesolution this nitrate is converted into the free base, which is finallycrystallized from ethyl-acetate. The yield is 15 gs: 16% of3amino-5-heptyltriazol1.2.4; melting point, 120 to 125 C.

Analysis.-Calculated: C:59.30%, l-l:9.95%, N: 30.74%. Found: C:59.64%,59.37%; H:9.95%, 9.87%; N:3l.1l%, 30.80%.

Remark: For anaiyzir' pu noses a small quantity of the sub-stance wasrecrystal zed from a mixture of alcohol Water (1:5); melting point, 134to 134.5 C. 9.1 rgs. of 5-n.hoptyi-E-amino-triazol-i2.4 g() moi), 4.6gs. of a mixti re or zx-, 5- and icoiine niol), 8.5 gs. of his (Nl-dimethylarnido)-phosphorylchloride /30 mol) and 50rn1s. of diethylether are heated at 60 to 70 C. whilst stirring, for 6 hours. theacetonitrii is evaporated in vacuo. The is extracted with ether. Theethereal solution is washed with 0.5 N hydrochloric acid and then withWater. The solution is dried and the ether evaeorated. The re due ispurifier via alumina. A yellow oil is obtained.

Yield, 31%.

Analysis.Calculated: P:9.79%, C:49.35%, H: 9.24%, N:26.56%. Found:P:9.4%; C: 7.76%, 48.61%; l-l:.34%, 9.49%; 14:26.40, 26.21%.

Example VII 86 gs. (0.5 mol) of amino-guanidine bisulphate (meltingpoint, 158 to 160 C.) is heated on an oil bath with 100 lgs. of lauricacid (0.5 moi) at 150 160 C., for hours. After the termina ion of thereaction the viscous, solid contents of the reaction vessel aretransferred with Water to a porcelain dish and neutralized withanhydrous sodium carbonate. On the vapour bath the solution isevaporated to dryness. The last remains of Water are removed in thevacuum dr ing chamber, after which the dry substance is pulverized andextracted With absolute alcohol. After cooling the sodium iauratecrystals which ernanatcsfrorn the unconverted lau-ric acid, the iaurateis filtered oft". Thc

residue obtainedi re 1 The yield is 38 gs.:32% of5uude-"yl-3-arn.no-triazol-' A mixture or 5.7 gs. of bislhlphorylchloride 11101) 7.9 gs. of

on 1e heated at 70 t tor 5 110111 s. UQC-l'l coolin '2 the hydrochloricacid sad i 2,6-diethyi-pyridine is separated out. it is filtered oil.The filtrate is washed, in succession, with Water, a solution of sodiumbicarbonate and again Water. The solution is dried and the benzeneevaporated in vacuo. The crystalline residue is recrystallized fromether. Yield, 47.5 C.

Analysis.Calculated: i:8.31%, C:5'4.81%, H: 10.01%, N:22.56%. Found:P:8.6%; C:55.07%, 54.61%; H:10.19%, 10.05%; N:22.33, 22.52%.

Example VIII 8 gs. of 5-phenyl-3-amino-triazol-1,2,4 moi) (Eenack,Dissert. Miinchen, 1896), 6.0 gs. of collidine moi) 8.5 gs. ofbis(N.N-dimethylarnido) phosphorylchloride mol) and rule. ofacetonit-ril are mixed and heated at to C., Whilst stirring, for 10hours. Then the acetonitr-il is removed by distillation in vacuo. Theresidue is extracted With benzene. The solution obtained is evaporatedin vacuo. The remaining crystalline mass is recrystallized from aqueousalcohol. Yield, 71%. Melting point, 167.5 to 168 C.

Analysis-Calculated: P:l0'.52%, C:48.97%, H: 6.51%, N:28.56%. Pound:i:10.7%; C:49.03%, 49.21%; H:6.5'i%, 6.55%; N:28.58, 28.61%.

Example IX A mixture of 86 gs. (0.5 mol) of amino-guanidine bisulphate(melting point, 158 to 160 C.), 68 gs. (0.5 mol) of phenyiacetic acid, 5rnls. of Water and a few drops of concentrated nitric acid is heated inan oil bath at to C., for 30 hours. After the termination of thereaction the clear solution is transferred with about 70 mls. of Waterto a porcelain dish, neutralized with 55 gs. of anhydrous sodiumcarbonate until the reaction was Weak alkaline. The solution obtained isevaporated to dryness and then extracted with, in total, 30 this. or"absolute alcohol. After filtration the alcohol is distilled off and theresidue is crystallized from water. The yield is 36 gs.:41% or"3-amino-5-ben zyl-triazoi- 1,2,4; melting point, 170 to 170.3'C. V

AnaIysz's.-Caiculated: C: 2.05%, l-l:5.78%, N: 32.16%. Found: C:62.52%,62.41%; i-l:5.96%, 5.59%; N:32.28%, 32.32%.

Whilst stirring, a mixture of 11.6 gs. of S-benzyl-S-v 7.10%, N:25.'75%.Found: P:9.6%, 9.9%; C:

25.32%. ExampleX A mixture of 36 gs. (0.5 moi) of an1ino-guanidinebisuiphate (melting point 158 to 160 C.), 74 gs o f transcinnainic acid(0.5 rnol) 5 mls. of Water and a few rops of concentrated nitric acid isheated an oil bath at to C., for 50 hour The mixture is then transferredwith 150 rnis. of Water toa porcelain dish, neutralized with anhydroussodium. carbonate and evaporated to dryness on a vapour bath. The drymass is ex: tracted with absolute alcohol, the alcohol isldistilie'd'ofipartly and after the addition ofethyl-acetate, the base is 1 The meltingpoint of'thev nitrate is, after recrystallisation from Water, about 260:

The free base is obtained therefrom by rneans ofithe l The substance."

converted into the nitrate.

C. calculated q. -ty of methanol/XOR is recrystallized frommethanol/water (2:5).

Melting point, 46.5 to V The solvent is then evaporated in 13 is gs.=5%of 3-amino-5-styryl-triazol-1,2,4; melting point, 231.5 to 233.5 C.

Analysis.-Calculated: C=64.49%, H=5.41%, N: 30.09%. Found: C=64.33%,64.54%; H=5.53%, 5.75%; N=29.84%, 29.87%.

4.9 gs. of 3-arnino-5-styryl-triazol-l,2,4 (0.026 mol), 3.2 gs. ofcollidine (0.026 mol), 4.5 gs. or bis(N.N-dimethylarnido)phosphorylchloride (0.025 mol) and 50 mls. oi acetonitril are heated,whilst stirring, at 60 to 70 C. for 17 hours. Then the acetonitril isdistilled off in vacuo. The residue is extracted with benzene. Thecrystalline substance, which separates out during the distillation ofbenzene, is isolated by filtration and recrysta lized from ligroine.

Yield, 58%. Melting point, 149.5 to 152.5 C.

AnaIysis.Calculated: P=9.67%, C= 2.49%, H: 6.61%, N==26.23%. Found:P=l0.0%; C:52.44%, 52.46%; H=6.77%, 6.64%; N=25.87%, 25.95%.

Example XI To a mixture of 4.2 gs. of 3-amino-triazol-1,2,4 mol) 6.0 gs.of collidine mol) and 50 mls. of acetonitril is added 11.3 gs. ofbis(N.N-diethylarnido)phosphorylchloride mol). The mixture obtained isheated at 70 to 80 C., whilst stirring, for 7 hours. Then theacetonitril is evaporated in vacuo. The residue is extracted withbenzene. The solution in benzene is inspissated; the mass obtained isrecrystallized from water.

Yield, 53%. Melting point, 105 to 106 C.

For analyzing purpose a small quantity is recrystallized from water.Melting point, 106 to 106.5

Analysis.Calculated: P=11.29%, C=43.78%, H: 8.45%, N=30.64%. Found:P=11.3%; C=43.66%, 43.61%; H=8.65%, 8.70%; N=30.11%, 30.36%.

Example XII 6.3 gs. of bis(N.N-diethylamido)phosphorylchloride (0.28mol) is added, whilst stirring, to a mixture of 4.2 gs. of5n-pentyl-3-amino-triazol-1,2,4 (0.28 mol) 3.4 gs. of collidine (0.28mol) and 40 mls. of ether. The mixture is heated at 70 to 75 C., Whilststirring, for 6 hours. Then the acetonitril is removed by distillationin vacuo and the residue is extracted with ether. The ethereal so lutionis Washed with Water, dried and inspissated. The residue is dissolved inpetroleum ether. This solution is washed with Water and after drying, itis inspissated. An oil is obtained, which crystallizes after some time.Yield, 87%.

Analysis.Calculated: P=8.99%.

Example XIII A mixture of 16.8 gs. of 3-amino-triazol-1.2.4 (2.10 mol),18.65 gs. of bis(N.N-diinethylamido)thiophosphorylchloride mol) and 300rnls. of acetonitrii is heated at 65 to 70 C., whilst continuouslystirring, for 8 hours. The acetonitril is then removed by distillationin vacuo. T o the solid residue water is added. The part not soluble inwater is filtered off and crystallized from water. Yield, 22%. Meltingpoint, 120 to 121 C.

Analysis.-Calculated: P:13.22%, Found: P=13.1%, S=13.5%.

Example XIV In 25 mls. o1 anhydrous pyridine is dissolved 7.7 gs. of'3-amino-5-n.-pentyltriazol-1.2.4 (0.05 mol). To the solution is addedin drops 93 gs. of bis(N.N-dimethylamid thiophosphorylchloride (0.05mol). The mixture is then evaporated in vacuo and to the residue Wateris added. The oil obtained is extracted with ether. The ethereal extractis Washed with water, dried and inspissated. The residue is acrystalline product. Yield, 65%. Melting point, 139 to 140 C.

Alzalysis.Calculated: P=10.18%, C=43.40%, H: 8.28%, N=27.61%, 8:10.53.Found: P:10.3%; C:

Found: ?=9.1%.

43.90%, 43.51%; H=8.32%, 8.31%; N=26.35%, 26.89%; S=10.67%, 10.63%.

14 Example XV 7.78 gs. of 5-(4'-chloro-pheny1)-3-an1ino-triazol-1.2.4(0.04 mol) (Hoggarth, J. Chem. Soc. (1950), 612,), 4.84 gs. of collidine(0.04 mol) and 6.62 gs. of his (N.N-dimethylamido)-phosphorylchlorideare mixed with 100 mls. of acetonitril. The mixture is stirred at atemperature between 7 0 and C. for six hours. Then the acetonitril isevaporated in vacuo. The residue is extracted a few times with hotbenzene. The benzene is evaporated; the crystalline product obtained isrecrystallized from a mixture of ethanol and Water.

Yield: 73%. Melting point: 170 to 171 C.

Analysis.C-alc.: C:43.84%, H=5.52%, N=25.56%, Cl=10.79%, P=9.42%. Found:C=44.20%, 44.50%; H:5.81%, 5.88%; N=26.17%, 26.33%; Cl=11.03%, 11.11%;P=9.4%.

Example XVI 5.7 gs. of 5-(4'-methoxyphenyl)-3-amino-triazol-1.2.4 (0.03mol) (Hoggarth, J. Chem. Soc. (1950), 612), 4 gs. of collidine (0.03mol) and 5.1 gs. of his (N.N-dimethylamido)-phosphorylchloride (0.03mol) are joined in 100 mls. of acetonitril. The mixture is then stirredat a temperature of 75 to C. for six hours. Then the acetonitril isremoved by evaporation in vacuo. The residue is extracted a few timeswith dry benzene. The benzene is evaporated and the remainingcrystalline product is recrystallized from a mixture of water andalcohol (1:3).

Yield: 72%. Melting point: 173 to 174 C.

Analysis.Calc.: C=48.14%, H=6.52%, N=25.91%, P=9.55%. Found: C=48.46%,48.64%; H=6.58%, 7.11%; N:25.50%, 25.52%; P=9.55%.

Example XVII 7.8 gs. of 5-carbaethoxy-3amino-triazol-1.2.4 (0.05 mol)(Thiele Manchot, Ann. 303 54 (1898)) 6.0 gs. of collidine (0.05 mol) and8.5 gs. of his (N.N-dimethylamido)-phosphorylchloride (0.05 mole) aremixed with mls. of acetonitril. The mixture is heated, whilst stirring,at 50 to 60 C. for 24 hours. Then the acetonitril is removed byevaporation. The residue is extracted with cold water and then with amixure of acetone and ethanol. The acetone and the ethanol areevaporated. The re maining crystalline product is recrystallized fromwater.

Yield: 51%. Melting point: 151 to 153 C.

Amzlysis.Calc.: P=10.67%, C=37.24%, H=6.60%, N=28.95%. Found: P=10.3%;C=36.61%, 36.64%; H=6.57%, 6.59%; N=28.94%, 29.16%.

Example XVIII 23.6 gs. of S-amino-triazol-1.2.4-carboxylic acid-5 (0.185mol) is dissolved in 75 mls. of n.pentanol. Dry HCl-gas is passedthrough the solution; then the solution is boiled for 6 hours. Thenpentanol is removed by evaporation in vacuo. The residue is extractedwith cold water and then crystallized from a mixture of ethanol andwater.

Yield: 26%. Melting point: 168 to 169 C. (S-carb-npentoxy-3-an1inotriaz01-1 .2.4)

Aimlysis.Ca1c.: C=48.47%, H=7.12%, N== 8.27%. Found: C=46.92%, 47.20%;H=7.37%, 7.30%; N=27.63%, 27.35%.

7.92 gs. of 5-carb-n.pentoxy-3-amino-triazo1-1.2.4 (0.04 mol) 4.82 gs.of collidine and 682 gs. of his (N.N-diinethylamido)-phosphorylchloride(0.04 mol) are mixed With 75 hills. of acetonitril. The mixture isheated, whilst stirring, at 70 C. for six hours. The acetonitril isremoved by evaporation in vacuo. The residue is suspended in Water. Thecrystalline product is filtered ofi and recrystallized from ligroin.

Yield: 45%. Melting point: to 107 C.

Analysis.-Calc.: P=9.32%, C=43.37%, H:7.59%, N=25.29%. Found: P=9.27%;C=43.94%, 43.65%; H=7.65%; N=26.31%, 26.34%.

Example XXIX 8 gs. of -phenyl-3-amino-triaZol-1.2.4 (0.05 mol) and 50mls. of 30% by Weight of sodium hydroxide are joined. To the mixture isadded dripwise, Whilst stirring, gs. of his (N.N-dimethylarnido)-phosphorylchloride at a temperature of 5 to 10 C. The whole mixture isthen stirred again for 1.5 hours at a temperature of about 0 C. Then 100mls. of water is added. The precipitated crystalline product is filteredoff.

Yield: 22%. Melting point: 166 to 167 C.

What is claimed is:

1. An aminotriazole phosphorus compound of the formula wherein R R R Rare each alkyl of from 1 to 5 carbon atoms, X is a bivalent atomselected from the group consisting of sulfur and oxygen, R is3-aminotriazole 1,2,4 where n the 5 carbon is directly joined to amember of the group consisting of hydrogen, phenyl, 4-ch1oro-phenyl,4-methoxy phenyl, styryl, alkyl of 1-8 carbon atoms and carbo-loweralkoxy and wherein the phosphorus is joined directly to a ring nitrogenof the triazole moiety.

2. Bis (dimethylamido) phosphoryl-5-phenyl-3-aminotriazoie-1,2,4 whereinthe phosphorus is directly attached to a ring nitrogen.

3. Bis (dimethylamido) phosphoryl-5-n-pentyl-3-aminotriazole-1,2,4wherein the phosphorus is directly attached to a ring nitrogen.

4. Bis (dimethylamido) phosphoryl-5-ethyl-3-aminotriazole-1,2,4 whereinthe phosphorus is directly attached to a ring nitrogen.

5. Bis (dimethylamido) phosphoryl-S-isopropyl-3-arninotriazole-1,2,4wherein the phosphorus is directly attached to a ring nitrogen.

6. Bis (dimethylarnido) phosphoryl-5-methyl-3-amino triazole-1,2,4wherein the phosphorus is directly attached to a ring nitrogen.

7. Bis (dimethylamido) phosphoryl-5-n-heptyl-3-aminotriazole-1,2,4wherein the phosphorus is directly attached to a ring nitrogen.

8. Bis (dimethylamido) phosphoryl-5-benzyl-3-aminotriazole-1,2,4 whereinthe phosphorus is directly attached to a ring nitrogen.

9. Bis (dimethylamido) phosphoryl-3-amiriotriazole- 1,2,4 wherein thephosphorus is directly attached to a ring nitrogen.

10. Bis (dimethylamido) thionophosphoryl-S-n-pentyl3-aminotriazole-1,2,4 wherein the phosphorus is directly attached to aring nitrogen.

References Cited in the file of this patent UNITED STATES PATENTS2,751,384 Coover et a1. June 19, 1956 2,752,392 Saul et al June 26, 19562,800,486 Grundmann et al July 23, 1957 2,822,313 Nolan et al Feb. 4,1958 2,824,823 Wolf Feb. 25, 1958 2,843,586 Melamed July 15, 19582,888,461 Klingsberg May 26, 1959 2,914,536 Hardy et al Nov. 24, 19593,008,941 Lynn Nov. 14, 1961 OTHER REFERENCES Doak et al.: J. Am. Chem.Soc., Volume 76, pages 16213 (1954).

Doak et al.: J. Am. Chem. 800., volume 77, pages 48256 (1955).

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3 l2lO9O February 11 1964 Martinus Johannes Koopmans et ale It is herebycertified that error appears in the above numbered patent requiringcorrection and that the said Letters Patent should read as correctedbelow.

Column 5 line 25 for "sodium" read sodium alcoholate column 7, line 11for "anti eryisphaceaes" read antierysiphaceaes column 11 line 6 for"28,98" read 2898% line 46, for "'47a76%" read 48q76% column 14,, line 3for "662" read 682 line 39 for "mole" read mol same column 14,, line 65for "682" read 6082 =G Signed and sealed this 27th day of October 19649(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Aitesting Officer Commissioner ofPatents

1. AN AMINOTRIAZOLE PHOSPHORUS COMPOUND OF THE FORMULA